The microwave spectrum of linalool, an acyclic monoterpene, was recorded for the first time in the range from 9 to 16 GHz. The only conformer observed under molecular beam conditions was assigned. Fitting the rotational spectrum with two different programs treating internal rotation yielded the rotational constants A = 1.64674020(46) GHz, B = 0.68219862(16) GHz, C = 0.61875100(20) GHz, and the centrifugal distortion constants. The standard deviation of the fit was close to experimental accuracy. A−E splittings due to the internal rotation of one methyl group could be resolved and the internal rotation barrier was determined to be 400.20(64) cm−1. The results from microwave spectroscopy were used to validate the molecular geometry obtained from quantum chemical calculations.